US5159110A - Process for recovering n-methyliminodiacetic acid from sodium sulfate - Google Patents
Process for recovering n-methyliminodiacetic acid from sodium sulfate Download PDFInfo
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- US5159110A US5159110A US07/782,847 US78284791A US5159110A US 5159110 A US5159110 A US 5159110A US 78284791 A US78284791 A US 78284791A US 5159110 A US5159110 A US 5159110A
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- sodium sulfate
- mother liquor
- acid
- temperature
- methyliminodiacetic acid
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 21
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 21
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 16
- 239000012452 mother liquor Substances 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 10
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- ZUCSYDIQCDIPLJ-UHFFFAOYSA-L disodium;2-[carboxylatomethyl(methyl)amino]acetate Chemical compound [Na+].[Na+].[O-]C(=O)CN(C)CC([O-])=O ZUCSYDIQCDIPLJ-UHFFFAOYSA-L 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000020477 pH reduction Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 18
- 241001139947 Mida Species 0.000 description 17
- 150000001413 amino acids Chemical class 0.000 description 13
- 238000001640 fractional crystallisation Methods 0.000 description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004471 Glycine Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910003556 H2 SO4 Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- -1 alkaline earth metal salt Chemical class 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DGVYUUZXRMENAJ-UHFFFAOYSA-N 2-[cyanomethyl(2-hydroxyethyl)amino]acetonitrile Chemical compound OCCN(CC#N)CC#N DGVYUUZXRMENAJ-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910004809 Na2 SO4 Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 239000004247 glycine and its sodium salt Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940029258 sodium glycinate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
Definitions
- This invention is directed to a process for preparing N-methyliminodiacetic acid, and in particular, a process for recovering the same from solutions of its disodium salt.
- amino acids such as glycine and B-alanine have been prepared by hydrolyzing the corresponding nitrile with an aqueous alkaline earth metal hydroxide to form an alkaline earth metal salt of the amino acid, and treating the alkaline earth metal salt with carbon dioxide to form the free amino acid, and recovering the amino acid.
- Another method of producing such amino acids includes treatment with sulfuric acid to convert the intermediate sodium salt (such as sodium glycinate in the case of glycine) to the free amino acid.
- the intermediate sodium salt such as sodium glycinate in the case of glycine
- Such a process results in the formation of sodium sulfate, which is difficult to separate from the free amino acid.
- first slurry which is a mixture of precipitated sodium sulfate and a first mother liquor.
- the temperature is such that the precipitation of the amino acid is prevented.
- the mother liquor is cooled to a temperature effective for precipitating the amino acid.
- the amino acid is separated and recovered, and the process is repeated.
- Methyliminodiacetic acid is of interest for photographic applications.
- Chemical Abstracts 111(8):67804u it is disclosed that a bleaching solution for bleaching an exposed photographic material contains Fe(III) complex salts of organic acids including methyliminodiacetic acid.
- Chemical Abstracts 93(6):588196e a bleaching solution comprised of FeCl 3 , KBr and methyliminodiacetic acid, adjusted to a pH of 6.0 with NH 3 , is disclosed.
- Chemical Abstracts 77(4):24608v the biodegradation of N-methyliminodiacetic acid in river water is disclosed.
- N-methyliminodiacetic acid is biodegradable, thus making its use highly desirable in terms of environmental concerns
- N-methyliminodiacetic acid is formed from its disodium salt by acidification with sulfuric acid, separation of the acid from the resulting sodium sulfate solution is problematic. None of the foregoing patents suggests the application of fractional crystallization for the separation of N-methyliminodiacetic acid from such solutions.
- MIDA N-methyliminodiacetic acid
- the resulting disodium salt solution has a pH of greater than about 11.
- a solution of the disodium salt of MIDA at a temperature of about 80° C. is acidified with sulfuric acid to a pH of approximately 2 (about the isoelectric point of MIDA).
- the acidified solution is then concentrated to remove water and to simultaneously crystallize anhydrous sodium sulfate.
- the concentration step is carried out at a temperature sufficient to prevent the co-precipitation of MIDA. (The saturation temperature of MIDA will depend upon the original concentration of MIDANa 2 in the starting solution).
- the precipitated anhydrous sodium sulfate is separated from the hot slurry and the resulting first mother liquor is cooled to a temperature effective for precipitating N-methyliminodiacetic acid in a second mother liquor while avoiding the precipitation of anhydrous sodium sulfate or sodium sulfate decahydrate.
- the temperature to which the first mother liquor is cooled is just above the transition temperature (approximately 32.4° C.) of sodium sulfate/sodium sulfate decahydrate. A temperature of about 35° C. has been found to be suitable.
- the precipitated acid is separated and recovered from the second mother liquor, and the latter may then be recycled to an appropriate earlier stage in the process such as the concentration step, and the process repeated.
- the aforementioned separations of the precipitated sodium sulfate and MIDA are preferably accomplished by centrifugation, although other forms of separation such as filtration or decantation could be used.
- purge liquor from the fractional crystallization scheme can be cooled to a temperature low enough to precipitate, in the same mother liquor, both MIDA and sodium sulfate decahydrate.
- the resulting precipitate which is a mixed wet cake of MIDA and sodium sulfate decahydrate (Glauber's salt) can be separated from its mother liquor by centrifugation, and recycled to an earlier point in the production process of MIDANa 2 . Water can be added to the cake to form a pumpable stream. All or a portion of the mother liquor can be recycled to the MIDA/sodium sulfate decahydrate crystallizer to reduce the slurry density.
- Appropriate seeding may be carried out to initiate or enhance the various crystallizations.
- MIDANa 2 solution 1000 grams was added to a stainless steel beaker and 280 grams of H 2 O was charged. Starting at ambient temperature, a total of 639.5 grams of 50% H 2 SO 4 was added to lower the pH to 2.0. The temperature rose during the addition to about 65° C. With vigorous stirring and a gas burner, the solution was concentrated by boiling to 1114 grams. The resulting 80°-90° C. material was placed into a plastic 2 liter graduate. 200 ml. of crystals out of 720 ml. settled to the bottom. The material was then centrifuged hot (the centrifuge was heated with steam). 755.7 grams of liquor and 203.2 grams of sodium sulfate were recovered.
- the recovered liquor was cooled to 35° C. and allowed to stir at 35° C. overnight. During this time, 114.6g of water was lost by evaporation, thereby providing a slurry weighing 641.lg the next morning. The slurry was centrifuged at 35° C. and washed with water. 441.6 grams of liquor, 113.6 grams of MIDA and 172.6 grams of washings were recovered.
- the hot liquor was cooled to 35° C., placed in a 35° C. water bath, and stirred overnight.
- the slurry formed was centrifuged in the previously warmed centrifuge.
- the MIDA crystals were washed with approximately 10 ml. of water.
- the liquor was recycled to the next crystallization, and the process was repeated for a total of 15 cycles. No deterioration of crystallinity was observed and no solids/liquids separation problems arose.
- the liquor from the 15th cycle was carried through one more cycle in which no fresh MIDANa 2 was added. No crystallization problems occurred in this cycle. The absence of crystallization problems suggests that additional cycles would increase yield.
- Table 1 reports the data obtained from the foregoing.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
N-methyliminodiacetic acid is separated from mixtures of N-methyliminodiacetic acid and sodium sulfate formed by acidification of solutions of its disodium salt with sulfuric acid. Thus the disodium salt is acidified with sulfuric acid to a ph of about 2 and concentrated by evaporating water so as to crystallize sodium sulfate. The sodium sulfate is separated, and the resulting mother liquor is cooled to precipitate N-methyliminodiacetic acid, which is then separated.
Description
This is a Continuation-in-part of application Ser. No. 07/701,285, filed May 16, 1991.
This invention is directed to a process for preparing N-methyliminodiacetic acid, and in particular, a process for recovering the same from solutions of its disodium salt.
In the prior art, amino acids such as glycine and B-alanine have been prepared by hydrolyzing the corresponding nitrile with an aqueous alkaline earth metal hydroxide to form an alkaline earth metal salt of the amino acid, and treating the alkaline earth metal salt with carbon dioxide to form the free amino acid, and recovering the amino acid.
Another method of producing such amino acids includes treatment with sulfuric acid to convert the intermediate sodium salt (such as sodium glycinate in the case of glycine) to the free amino acid. However, such a process results in the formation of sodium sulfate, which is difficult to separate from the free amino acid.
U.S. Pat. Nos. 3,904,585 and 3,947,496 to Thunberg et al., the disclosures of which are incorporated by reference, disclose a process for separating glycine or B-alanine from such sodium sulfate solutions by fractional crystallization. Specifically, in the starting aqueous solution of sodium sulfate and the amino acid, which has a temperature above 33° C., a pH of 4.5-8.5, a mole ratio of amino acid to sodium sulfate of 1-5:1, and containing at least 5% of the amino acid, water is evaporated at a temperature of from 60° C. or 70° C. to about the normal boiling point in order to form a first slurry which is a mixture of precipitated sodium sulfate and a first mother liquor. The temperature is such that the precipitation of the amino acid is prevented. Upon separation of the precipitated sodium sulfate, the mother liquor is cooled to a temperature effective for precipitating the amino acid. The amino acid is separated and recovered, and the process is repeated.
U.S. Pat. No. 3,808,269 to Bragdon et al. discloses a similar process, except that iminodiacetic acid is separated from sodium sulfate solutions.
Methyliminodiacetic acid is of interest for photographic applications. In Chemical Abstracts 111(8):67804u, for example, it is disclosed that a bleaching solution for bleaching an exposed photographic material contains Fe(III) complex salts of organic acids including methyliminodiacetic acid. Similarly, in Chemical Abstracts 93(6):588196e, a bleaching solution comprised of FeCl3, KBr and methyliminodiacetic acid, adjusted to a pH of 6.0 with NH3, is disclosed. In Chemical Abstracts 77(4):24608v, the biodegradation of N-methyliminodiacetic acid in river water is disclosed.
Although other, perhaps more effective, chelating agents exist, N-methyliminodiacetic acid is biodegradable, thus making its use highly desirable in terms of environmental concerns However, where N-methyliminodiacetic acid is formed from its disodium salt by acidification with sulfuric acid, separation of the acid from the resulting sodium sulfate solution is problematic. None of the foregoing patents suggests the application of fractional crystallization for the separation of N-methyliminodiacetic acid from such solutions.
The problems of the prior art have been solved by the instant invention, which provides a process for separating and recovering N-methyliminodiacetic acid ("MIDA") from sodium sulfate solutions by fractional crystallization, either batchwise or continuously.
N-methyliminodiacetic acid can be formed from its disodium salt by acidification with sulfuric acid. The disodium salt can be formed by alkaline hydrolysis of N-methyliminodiacetonitrile ("MIDAN") by saponification with sodium hydroxide. The synthesis of MIDAN is described by Eschweiler, Annelen, 279, 41, of which the disclosure is incorporated herein by reference, as follows:
CH.sub.3 NH.sub.2 +2HOCH.sub.2 CN→CH.sub.3 N(CH.sub.2 CN).sub.2 +2H.sub.2 O
Indeed, analogous chemistry has been applied to the preparation of N-ethyliminodiacetonitrile, as described in J.A.C.S. 80, 5944 (1958), the disclosure of which is herein incorporated by reference, and to the preparation of 2-hydroxyethyliminodiacetonitrile, as described in U.S. Pat. No. 3,864,378, the disclosure of which is herein incorporated by reference.
Upon alkaline hydrolysis of the MIDAN, the resulting disodium salt solution has a pH of greater than about 11. In the preferred embodiment of the present invention, a solution of the disodium salt of MIDA at a temperature of about 80° C. is acidified with sulfuric acid to a pH of approximately 2 (about the isoelectric point of MIDA). The acidified solution is then concentrated to remove water and to simultaneously crystallize anhydrous sodium sulfate. The concentration step is carried out at a temperature sufficient to prevent the co-precipitation of MIDA. (The saturation temperature of MIDA will depend upon the original concentration of MIDANa2 in the starting solution). The precipitated anhydrous sodium sulfate is separated from the hot slurry and the resulting first mother liquor is cooled to a temperature effective for precipitating N-methyliminodiacetic acid in a second mother liquor while avoiding the precipitation of anhydrous sodium sulfate or sodium sulfate decahydrate. Preferably the temperature to which the first mother liquor is cooled is just above the transition temperature (approximately 32.4° C.) of sodium sulfate/sodium sulfate decahydrate. A temperature of about 35° C. has been found to be suitable. The precipitated acid is separated and recovered from the second mother liquor, and the latter may then be recycled to an appropriate earlier stage in the process such as the concentration step, and the process repeated.
The aforementioned separations of the precipitated sodium sulfate and MIDA are preferably accomplished by centrifugation, although other forms of separation such as filtration or decantation could be used.
The concentration of MIDANa2 in the starting solution must be in a range so that upon acidification, sodium sulfate is not co crystallized. Those skilled in the art will also appreciate that the temperature at which the acid precipitates is a function of the original concentration of the disodium salt, and thus either can be adjusted accordingly. Preferably the MIDANa2 feedstock for the fractional crystallization is about a 30% MIDANa2 solution.
In an additional embodiment, purge liquor from the fractional crystallization scheme can be cooled to a temperature low enough to precipitate, in the same mother liquor, both MIDA and sodium sulfate decahydrate. The resulting precipitate, which is a mixed wet cake of MIDA and sodium sulfate decahydrate (Glauber's salt), can be separated from its mother liquor by centrifugation, and recycled to an earlier point in the production process of MIDANa2. Water can be added to the cake to form a pumpable stream. All or a portion of the mother liquor can be recycled to the MIDA/sodium sulfate decahydrate crystallizer to reduce the slurry density.
Appropriate seeding may be carried out to initiate or enhance the various crystallizations.
The instant invention will be better understood by referring to the following specific but non-limiting examples. It is understood that modifications can be made without departing from the spirit and scope of the present invention.
1000 grams of MIDANa2 solution (approximately 41.2%) was added to a stainless steel beaker and 280 grams of H2 O was charged. Starting at ambient temperature, a total of 639.5 grams of 50% H2 SO4 was added to lower the pH to 2.0. The temperature rose during the addition to about 65° C. With vigorous stirring and a gas burner, the solution was concentrated by boiling to 1114 grams. The resulting 80°-90° C. material was placed into a plastic 2 liter graduate. 200 ml. of crystals out of 720 ml. settled to the bottom. The material was then centrifuged hot (the centrifuge was heated with steam). 755.7 grams of liquor and 203.2 grams of sodium sulfate were recovered.
The recovered liquor was cooled to 35° C. and allowed to stir at 35° C. overnight. During this time, 114.6g of water was lost by evaporation, thereby providing a slurry weighing 641.lg the next morning. The slurry was centrifuged at 35° C. and washed with water. 441.6 grams of liquor, 113.6 grams of MIDA and 172.6 grams of washings were recovered.
The feedstock was a 31.9% solution of MIDANa2. To a 2 liter graduated Pyrex beaker was added 1.00 kg of MIDANa2 and sufficient water to give a 30% MIDANa2 solution To this was added liquor from a previous cycle. 93% H2 SO4 was added to a pH of 2.0 while cooling to keep the temperature less than or equal to 60° C. This solution was boiled until the volume percent of settled crystals was approximately 20%. The centrifuge was heated with steam and then the hot slurry (greater than 80° C.) was separated. The Na2 SO4 cake was not washed before being dried.
The hot liquor was cooled to 35° C., placed in a 35° C. water bath, and stirred overnight. The slurry formed was centrifuged in the previously warmed centrifuge. The MIDA crystals were washed with approximately 10 ml. of water. The liquor was recycled to the next crystallization, and the process was repeated for a total of 15 cycles. No deterioration of crystallinity was observed and no solids/liquids separation problems arose. The liquor from the 15th cycle was carried through one more cycle in which no fresh MIDANa2 was added. No crystallization problems occurred in this cycle. The absence of crystallization problems suggests that additional cycles would increase yield. Table 1 reports the data obtained from the foregoing.
TABLE I
__________________________________________________________________________
Summary of Data from Cyclic MIDA Fractional Crystallization
__________________________________________________________________________
Experiments
Weight
Materials Charged Weights Gms
Gms Gms Before
Cycle Liquor &
Before
After
% Boiled
Cool
No. MIDA No.sub.2
H.sub.2 O Added
93% H.sub.2 SO.sub.4
Wash Boil-off
Boil-off
off Down
__________________________________________________________________________
1 1000 383 186 0 1569 1251 20.3 1047
2 1000 383 298 903 2584 1964 24 1524
3 1000 383 233 936 2553 2029 20.5 1704
4 1000 383 267 1384 3034 2391 21.2 2006
5 1000 383 200 1475 3058 2458 19.6 2201
6 1000 383 279 1994 3656 2916 20.2 2414
7 1000 383 224 1652 3259 2578 21.1 2168
8 1000 383 423 1593 3399 2718 20.1 2311
9 1000 383 258 1683 3323 2425 27.0 1922
10 1000 383 235 1029 2647 2117 20.0 1787
11 1000 383 305 1340 3029 2324 23.3 1937
12 1000 383 224 657 2264 1754 22.5 1447
13 1000 383 250 1080 2713 2141 21.1 1793
14 1000 383 250 1240 2868 2224 22.5 1866
15 1000 383 278 1353 3014 2314 23.2 1907
16 1000 383 116 1220 1336 1051 21.4 860
17
18
__________________________________________________________________________
Contained
MIDA Gms of Contained
Charged Materials Recovered
MIDA Cumula-
Cycle
This
Cumula-
MIDA,
Na.sub.2 SO.sub.4
Liquid &
% This
Cumula-
tive
No. Cycle
tive gms gms Wash, gms
A.I.
Cycle
tive % Yield
__________________________________________________________________________
1 319 319 0 154 903 0 0 0
2 319 638 398 344 9362 94.0
374 374 58.6
3 319 957 193 248 1384 87.9
169 543 56.7
4 319 1276 309 291 1475 95.7
296 839 65.8
5 319 1595 70 253 1994 98.6
69 908 56.9
6 319 1914 466 347 1652 91.1
425 1333 69.6
7 319 2233 28 319 1593 79.0
226 1559 69.8
8 319 2552 342 299 1683 95.4
326 1885 73.9
9 319 2871 511 384 1029 82.9
424 2309 80.4
10 319 3190 253 241 1340 84.6
214 2523 79.1
11 319 3509 592 292 657 66.0
391 2914 83.0
12 319 3828 228 225 1080 77.3
176 3090 80.7
13 319 4147 315 240 1240 82.1
259 3349 80.8
14 319 4466 309 265 1353 86.3
267 3616 81.0
15 319 4785 342 341 1277 94.3
323 3939 82.3
16 319 4785 122 139 649 80.2
98 4037 84.4
17 4737 4382*
18
__________________________________________________________________________
*MIDA in composite sample = 2.2%
Claims (5)
1. A process for recovering N-methyliminodiacetic acid from solutions comprising disodium N-methyliminodiacetate and sodium sulfate, comprising:
a. adjusting the pH of said solution to about 2 with sulfuric acid;
b. concentrating the pH adjusted solution to remove water and form a first slurry comprising crystallized anhydrous sodium sulfate and a first mother liquor;
c. separating the crystallized anhydrous sodium sulfate from said mother liquor;
d. adjusting the temperature of said first mother liquor so as to form a second slurry comprising precipitated N-methyliminodiacetic acid and a second mother liquor; and
e. separating the precipitated N-methyliminodiacetic acid from said second mother liquor.
2. A process according to claim 1, wherein said solution is concentrated by evaporating water.
3. A process according to claim 1, wherein the temperature of said first mother liquor is adjusted by lowering the temperature thereof to just above the transition temperature of sodium sulfate and sodium sulfate decahydrate.
4. A process according to claim 1, further comprising recycling said second mother liquor.
5. A process according to claim 1, further comprising cooling said second mother liquor to a temperature effective for forming a slurry comprising a mixture of precipitated N-methyliminodiacetic acid and sodium sulfate decahydrate in a third mother liquor, and separating the precipitated N-methyiminodiacetic acid and sodium sulfate decahydrate from said third mother liquor.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/782,847 US5159110A (en) | 1991-05-16 | 1991-10-24 | Process for recovering n-methyliminodiacetic acid from sodium sulfate |
| CA002068396A CA2068396A1 (en) | 1991-05-16 | 1992-05-11 | Process for recovering n-methyliminodiacetic acid from sodium sulfate solutions |
| EP92304347A EP0514169B1 (en) | 1991-05-16 | 1992-05-14 | Process for recovering N-methyliminodiacetic acid from sodium sulfate solutions |
| DE69206877T DE69206877T2 (en) | 1991-05-16 | 1992-05-14 | Process for the recovery of N-methyliminodiacetic acid from solutions containing sodium sulfate |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70128591A | 1991-05-16 | 1991-05-16 | |
| US07/782,847 US5159110A (en) | 1991-05-16 | 1991-10-24 | Process for recovering n-methyliminodiacetic acid from sodium sulfate |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US70128591A Continuation-In-Part | 1991-05-16 | 1991-05-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5159110A true US5159110A (en) | 1992-10-27 |
Family
ID=27106762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/782,847 Expired - Lifetime US5159110A (en) | 1991-05-16 | 1991-10-24 | Process for recovering n-methyliminodiacetic acid from sodium sulfate |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5159110A (en) |
| EP (1) | EP0514169B1 (en) |
| CA (1) | CA2068396A1 (en) |
| DE (1) | DE69206877T2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6320061B1 (en) | 2000-06-05 | 2001-11-20 | Eastman Chemical Company | Solvent exchange process |
| US6670505B1 (en) | 2000-03-07 | 2003-12-30 | Eastman Chemical Company | Process for the recovery of organic acids from aqueous solutions |
| US20090234160A1 (en) * | 2006-07-19 | 2009-09-17 | Ichiro Fujita | Process for producing succinic acid |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1493723A (en) * | 1966-07-21 | 1967-09-01 | Air Liquide | Process for preparing sodium dipersulfate |
| US3463812A (en) * | 1967-11-17 | 1969-08-26 | Grace W R & Co | Process for preparing dialkali metal iminodiacetate |
| US3510515A (en) * | 1970-03-09 | 1970-05-05 | Chatten Drug & Chem Co | Method of making glycine |
| US3808269A (en) * | 1972-12-29 | 1974-04-30 | Grace W R & Co | Process for recovering iminodiacetic acid from sodium sulfate solutions |
| US3852344A (en) * | 1972-12-29 | 1974-12-03 | Grace W R & Co | Process for recovering iminodiacetic acid from sodium chloride solutions |
| US3904585A (en) * | 1974-02-14 | 1975-09-09 | Grace W R & Co | Process for recovering glycine and beta-alanine from sodium sulfate solutions |
| US3932501A (en) * | 1974-10-24 | 1976-01-13 | W. R. Grace & Co. | Process for recovering beta-alanine from sodium chloride solutions |
| US3947496A (en) * | 1974-10-24 | 1976-03-30 | W. R. Grace & Co. | Process for recovering glycine from sodium sulfate solutions |
| GB1472840A (en) * | 1974-09-18 | 1977-05-11 | Showa Denko Kk | Method of separating and purifying glycine |
| JPS5673620A (en) * | 1979-11-19 | 1981-06-18 | Tokuyama Soda Co Ltd | Separation of sodium sulfate and sodium chloride from mixed solution of sodium chloride and sodium sulfate |
| US4299978A (en) * | 1979-04-04 | 1981-11-10 | Showa Denko Kabushiki Kaisha | Process for separating iminodiacetic acid from aqueous glycine solution |
| US4306880A (en) * | 1978-09-22 | 1981-12-22 | Garrett Donald E | Recovering by-products from sea water brines and the like |
| EP0081063A1 (en) * | 1981-11-10 | 1983-06-15 | FMC Corporation | Method for producing sodium persulfate |
| US4691054A (en) * | 1985-09-13 | 1987-09-01 | Ajinomoto Co., Inc. | Method for separating a basic amino acid |
| US4818409A (en) * | 1985-04-20 | 1989-04-04 | Basf Aktiengesellschaft | Obtaining aqueous solutions of organic acids or bases from aqueous solutions of their salts |
| US4986976A (en) * | 1989-04-11 | 1991-01-22 | W. R. Grace & Co.-Conn. | Recovery of glycine and glauber's salt from waste crystal liquors |
| US5011988A (en) * | 1989-10-11 | 1991-04-30 | W. R. Grace & Co.-Conn. | Recovery of IDA and Glauber's salt from waste crystal liquors |
| JPH05313609A (en) * | 1992-05-13 | 1993-11-26 | Seiko Epson Corp | Liquid crystal drive |
-
1991
- 1991-10-24 US US07/782,847 patent/US5159110A/en not_active Expired - Lifetime
-
1992
- 1992-05-11 CA CA002068396A patent/CA2068396A1/en not_active Abandoned
- 1992-05-14 EP EP92304347A patent/EP0514169B1/en not_active Expired - Lifetime
- 1992-05-14 DE DE69206877T patent/DE69206877T2/en not_active Expired - Fee Related
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1493723A (en) * | 1966-07-21 | 1967-09-01 | Air Liquide | Process for preparing sodium dipersulfate |
| US3463812A (en) * | 1967-11-17 | 1969-08-26 | Grace W R & Co | Process for preparing dialkali metal iminodiacetate |
| US3510515A (en) * | 1970-03-09 | 1970-05-05 | Chatten Drug & Chem Co | Method of making glycine |
| US3808269A (en) * | 1972-12-29 | 1974-04-30 | Grace W R & Co | Process for recovering iminodiacetic acid from sodium sulfate solutions |
| US3852344A (en) * | 1972-12-29 | 1974-12-03 | Grace W R & Co | Process for recovering iminodiacetic acid from sodium chloride solutions |
| US3904585A (en) * | 1974-02-14 | 1975-09-09 | Grace W R & Co | Process for recovering glycine and beta-alanine from sodium sulfate solutions |
| GB1472840A (en) * | 1974-09-18 | 1977-05-11 | Showa Denko Kk | Method of separating and purifying glycine |
| US3985801A (en) * | 1974-10-24 | 1976-10-12 | W. R. Grace & Co. | Process for recovering glycine from sodium chloride solutions |
| US3947496A (en) * | 1974-10-24 | 1976-03-30 | W. R. Grace & Co. | Process for recovering glycine from sodium sulfate solutions |
| US3932501A (en) * | 1974-10-24 | 1976-01-13 | W. R. Grace & Co. | Process for recovering beta-alanine from sodium chloride solutions |
| US4306880A (en) * | 1978-09-22 | 1981-12-22 | Garrett Donald E | Recovering by-products from sea water brines and the like |
| US4299978A (en) * | 1979-04-04 | 1981-11-10 | Showa Denko Kabushiki Kaisha | Process for separating iminodiacetic acid from aqueous glycine solution |
| JPS5673620A (en) * | 1979-11-19 | 1981-06-18 | Tokuyama Soda Co Ltd | Separation of sodium sulfate and sodium chloride from mixed solution of sodium chloride and sodium sulfate |
| EP0081063A1 (en) * | 1981-11-10 | 1983-06-15 | FMC Corporation | Method for producing sodium persulfate |
| US4818409A (en) * | 1985-04-20 | 1989-04-04 | Basf Aktiengesellschaft | Obtaining aqueous solutions of organic acids or bases from aqueous solutions of their salts |
| US4691054A (en) * | 1985-09-13 | 1987-09-01 | Ajinomoto Co., Inc. | Method for separating a basic amino acid |
| US4986976A (en) * | 1989-04-11 | 1991-01-22 | W. R. Grace & Co.-Conn. | Recovery of glycine and glauber's salt from waste crystal liquors |
| US5011988A (en) * | 1989-10-11 | 1991-04-30 | W. R. Grace & Co.-Conn. | Recovery of IDA and Glauber's salt from waste crystal liquors |
| JPH05313609A (en) * | 1992-05-13 | 1993-11-26 | Seiko Epson Corp | Liquid crystal drive |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6670505B1 (en) | 2000-03-07 | 2003-12-30 | Eastman Chemical Company | Process for the recovery of organic acids from aqueous solutions |
| US6320061B1 (en) | 2000-06-05 | 2001-11-20 | Eastman Chemical Company | Solvent exchange process |
| US20090234160A1 (en) * | 2006-07-19 | 2009-09-17 | Ichiro Fujita | Process for producing succinic acid |
| US7915447B2 (en) * | 2006-07-19 | 2011-03-29 | Showa Denko K.K. | Process for producing succinic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69206877D1 (en) | 1996-02-01 |
| DE69206877T2 (en) | 1996-06-05 |
| CA2068396A1 (en) | 1992-11-17 |
| EP0514169A3 (en) | 1993-03-03 |
| EP0514169A2 (en) | 1992-11-19 |
| EP0514169B1 (en) | 1995-12-20 |
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